CN117924124A - Synthetic method of clean steering acid betaine surfactant - Google Patents
Synthetic method of clean steering acid betaine surfactant Download PDFInfo
- Publication number
- CN117924124A CN117924124A CN202410052683.9A CN202410052683A CN117924124A CN 117924124 A CN117924124 A CN 117924124A CN 202410052683 A CN202410052683 A CN 202410052683A CN 117924124 A CN117924124 A CN 117924124A
- Authority
- CN
- China
- Prior art keywords
- hydroxysulfobetaine
- fatty acid
- betaine surfactant
- synthesizing
- amide propyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002253 acid Substances 0.000 title claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 36
- 229960003237 betaine Drugs 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 31
- 229930195729 fatty acid Natural products 0.000 claims abstract description 31
- 239000000194 fatty acid Substances 0.000 claims abstract description 31
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 31
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 238000006266 etherification reaction Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000011033 desalting Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 3
- 239000012065 filter cake Substances 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000003113 alkalizing effect Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 5
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 5
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- HNFOAHXBHLWKNF-UHFFFAOYSA-M sodium;2-bromoethanesulfonate Chemical group [Na+].[O-]S(=O)(=O)CCBr HNFOAHXBHLWKNF-UHFFFAOYSA-M 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 2
- QRMLKVVWCJUMPR-UHFFFAOYSA-N BrCC[Na] Chemical compound BrCC[Na] QRMLKVVWCJUMPR-UHFFFAOYSA-N 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 7
- 229940117986 sulfobetaine Drugs 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- -1 carboxyl betaine Chemical compound 0.000 description 6
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- FWRSICGJFOGMSU-UHFFFAOYSA-N 2-oxooxetane-3-sulfonic acid Chemical compound S(=O)(=O)(O)C1C(=O)OC1 FWRSICGJFOGMSU-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012019 product validation Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention relates to a synthesis method of a clean steering acid betaine surfactant, which has the structural formula: The synthesis steps are as follows, firstly, the fatty acid amidopropyl hydroxysulfobetaine is dehydrated, desalted and purified in sequence, then etherification reaction is carried out in a solvent, freeze suction filtration is carried out, and the fatty acid amidopropyl disulfobetaine is obtained after the desalting and purification. The dissolution speed of betaine in acid liquid is increased, the salt resistance and the temperature resistance are improved, and the betaine has higher steering peak viscosity under the same formula condition.
Description
Technical Field
The invention relates to the field of industrial surfactant synthesis and oil-gas field acidification, in particular to a synthesis method of a clean turning acid betaine surfactant.
Background
The acidizing and fracturing transformation process technology is one of the leading technologies of increasing and stabilizing the yield of carbonate rock oil and gas reservoir development wells, and has become an essential and important means for finding oil and gas or exploring reserves of exploration wells. When the acid liquor encounters salts or the temperature rises, the spherical micelles are changed into worm-shaped micelles, and intertwined to generate viscoelastic liquid, so that the viscosity is improved, and the temporary blocking and steering effect of the acid liquor is realized. By optimizing the retarding performance of the acid liquor system, the acidification penetration distance can be increased to realize deep acidification, further reduce stratum injury and achieve the purpose of yield increase.
The clean diverting acid has the advantages of excellent diverting performance, good filtrate control performance, no harm to a reservoir and the like, so that the clean diverting acid is widely applied to uniform reformation of a carbonate reservoir. The currently applied diverting agent surfactants in self-diverting acid systems are of betaine type and rely on a large amount of Ca 2+、Mg2+ generated after the acid has reacted with the carbonate to rapidly increase the viscosity and thereby achieve diversion.
The surfactant for acidification is mainly betaine prepared from oleic acid or erucic acid, and is classified into carboxyl type
Sulfo group
Hydroxysulfonyl group
The Feng Yujun subject group carries out systematic study on the betaine surfactant, and discovers that the performance of the surfactant and the solution application performance thereof are determined by different hydrophilic group structures. The ammonium ion and carboxyl in the carboxyl betaine are separated by one methylene, so that stable inner salt cannot be formed (the ammonium ion and the oxyanion share four atoms, and the four-membered ring is unstable), and therefore, the solubility of the carboxyl betaine is good; the ammonium ions and the sulfonate groups in the sulfobetaine are separated by three methylene groups, so that an inner salt structure of a stable six-membered ring can be formed, and the hydroxysulfobetaine can also form an inner salt structure similar to the six-membered ring, so that the solubility is lower than that of the carboxybetaine; due to the introduction of hydroxyl groups, the hydrophilicity is increased, so that the solubility of the hydroxysulfobetaine is better than that of the sulfobetaine.
Because the sulfobetaine is used by the sulfopropiolactone method, the cost is high, and the industrialization application is difficult in the oilfield steering acidification process, the industrial application is carboxyl betaine and hydroxysulfobetaine, the oleic acid carboxyl betaine is used at the low temperature of 60-90 ℃, the erucic acid carboxyl betaine is used at the medium temperature of 90-120 ℃, and the erucic acid hydroxysulfobetaine is used at the high temperature of 120-150 ℃. There is therefore a need for betaines that improve the dissolution performance and salt and temperature resistance of clean turning acid surfactants.
Disclosure of Invention
Based on this, it is necessary to provide a synthetic method of a clean turning acid betaine surfactant in view of the above problems.
A method for synthesizing a clean turning acid betaine surfactant, wherein the betaine surfactant has the structural formula:
The synthesis steps are as follows, firstly, the fatty acid amidopropyl hydroxysulfobetaine is dehydrated, desalted and purified in sequence, then etherification reaction is carried out in a solvent, freeze suction filtration is carried out, and the fatty acid amidopropyl disulfobetaine is obtained after the desalting and purification.
Preferably, the fatty acid amidopropyl hydroxysulfobetaine is one of oleic acid amidopropyl hydroxysulfobetaine, stearic acid amidopropyl hydroxysulfobetaine and erucic acid amidopropyl hydroxysulfobetaine, the solid content is 40-50 wt%, and the isopropanol content is 20-30 wt%.
Preferably, the dehydration process comprises the steps of adding fatty acid amide propyl hydroxysulfobetaine and an organosilicon defoamer into a distillation flask, wherein the weight ratio of the fatty acid amide propyl hydroxysulfobetaine to the organosilicon defoamer is 900-1100:1, and carrying out rotary reduced pressure distillation for 1-5 h at 50-90 ℃ until no liquid is produced, thus obtaining yellow to succinic acid viscous paste.
Preferably, the desalting process comprises the steps of mixing dehydrated fatty acid amide propyl hydroxysulfobetaine with small molecular alcohol, heating to 40-80 ℃, stirring until the mixture is uniformly dispersed, filtering out inorganic salts while the mixture is hot, cooling to-10-0 ℃, filtering to obtain a pale yellow filter cake, and vacuum-drying the filter cake at low temperature for 4-24 hours to obtain purified fatty acid amide propyl hydroxysulfobetaine.
Preferably, the etherification reaction comprises the steps of mixing and stirring the purified fatty acid amide propyl hydroxysulfobetaine and a solvent uniformly, adding potassium hydroxide for alkalization for 1-4 h, heating to 60-90 ℃, dropwise adding an etherifying agent solution for 1-4 h, dropwise adding the etherifying agent solution for 1-4 h, continuing to react for 1-4 h, cooling to-10-0 ℃, performing suction filtration to obtain a light yellow filter cake, desalting with small molecular alcohol, performing suction filtration, and performing low-temperature vacuum drying for 4-24 h to obtain the purified fatty acid amide propyl disulfobetaine.
Preferably, the small molecular alcohol used in the desalting process step is one of methanol, ethanol and isopropanol, and the mass ratio of the small molecular alcohol to the fatty acid amide propyl hydroxysulfobetaine is 1-3:1.
Preferably, in the etherification reaction, the solvent used is one of diethylene glycol dimethyl ether and diethylene glycol diethyl ether and a mixture thereof, and the mass ratio of the solvent to the fatty acid amide propyl hydroxysulfobetaine is 1-3:1.
Preferably, in the etherification reaction, the mass ratio of the alkalizing agent potassium hydroxide to the fatty acid amidopropyl hydroxysulfobetaine used in the alkalizing step is 1 to 1.1:1.
Preferably, in the etherification reaction, the etherifying agent is sodium bromoethyl sulfonate, and the mass ratio of the etherifying agent to the fatty acid amide propyl hydroxysulfobetaine is 1-1.1:1.
The invention has the advantages that: the dissolution speed of betaine in acid liquid is increased, the salt resistance and the temperature resistance are improved, and the betaine has higher steering peak viscosity under the same formula condition.
Drawings
FIG. 1 is a rheological profile of a clean diverting acid formulated with an oleamide propyl bis-sulfobetaine surfactant;
FIG. 2 is a rheology curve of a comparative oleamide propylhydroxysulfobetaine surfactant formulated clean diverting acid;
FIG. 3 is a rheology profile of a clean diverting acid formulated with erucamide propyl disulfobetaine surfactant;
Fig. 4 is a rheological profile of a clean diverting acid formulated with erucamide propyl hydroxysulfobetaine surfactant.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
500G of stearic acid amide propyl hydroxysulfobetaine and 0.5g of organic silicon defoamer are weighed, distilled under reduced pressure at 60 ℃ for 1h, heated to 90 ℃ after the first distillation under reduced pressure, and distilled under reduced pressure again for 2h to obtain light 165g of amber paste. The reduced pressure distillation is particularly a distillation operation performed at a pressure lower than atmospheric pressure, and can be used for separating and purifying organic compounds with high boiling point and poor thermal stability, thereby completing the dehydration operation.
Further, 350g of methanol is added, reflux magnetic stirring is carried out for 2 hours at 50 ℃ in water bath, inorganic salts are removed by suction filtration at 50 ℃, and the filtrate is collected and placed in a refrigerator at-10 ℃ for overnight; filtering at low temperature to obtain a pale yellow filter cake, and drying the filter cake at low temperature in vacuum for 12 hours to obtain 145g of purified stearamidopropyl hydroxysulfobetaine, namely completing desalting operation.
The etherification reaction is carried out by taking 44.31g of sodium bromoethyl sulfonate (210 mmol) and 50g of diethylene glycol dimethyl ether, stirring and dissolving uniformly to obtain 50% solution bromoethyl sodium sulfonate solution; weighing 101.2g (200 mmol) of purified stearic acid amide propyl hydroxysulfobetaine and 200g of diethylene glycol diethyl ether, uniformly mixing and stirring, then adding 11.76g (210 mmol) of potassium hydroxide, heating to 60-90 ℃ and alkalizing for 1h; dropwise adding a bromoethyl sodium sulfonate solution for 1.5h, continuously reacting for 3h after dropwise adding, cooling to room temperature, placing in a refrigerator at-10 ℃ for 8h, and performing suction filtration to obtain a light yellow filter cake; 200g of absolute alcohol and a filter cake are weighed and added into a 500mL single-neck flask, the mixture is stirred magnetically for 2 hours at 70 ℃ in a water bath under reflux, a yellow filter cake is obtained by suction filtration at 70 ℃, the filter cake is dried in vacuum for 24 hours at a low temperature, and 105.9g of purified stearamidopropyl disulfobetaine is obtained, and the yield is 85.4%.
Example two
500G of oleamide propyl hydroxysulfobetaine and 0.5g of organic silicon defoamer are weighed, distilled for 1h under reduced pressure at 60 ℃, heated to 90 ℃ and distilled for 2h under reduced pressure, so as to obtain light 195g of amber paste; adding 400g of absolute ethyl alcohol, refluxing in a water bath at 70 ℃ and magnetically stirring for 2 hours, removing inorganic salts by suction filtration at 70 ℃, collecting filtrate, and placing in a refrigerator at-10 ℃ for overnight; filtering at low temperature to obtain a light yellow filter cake, and drying the filter cake at low temperature in vacuum for 12 hours to obtain 175g of purified oleamide propyl hydroxysulfobetaine.
The etherification reaction is carried out by taking 42.2g of bromoethyl sodium sulfonate (200 mmol) and 50g of diethylene glycol dimethyl ether, stirring and dissolving uniformly to obtain 50% solution bromoethyl sodium sulfonate solution; weighing 100.8g (200 mmol) of purified oleic acid amide propyl hydroxysulfobetaine and 150g of diethylene glycol dimethyl ether, uniformly mixing and stirring, then adding 11.2g (200 mmol) of potassium hydroxide, heating to 60-90 ℃ and alkalizing for 1h; dropwise adding a bromoethyl sodium sulfonate solution for 2 hours, continuously reacting for 2 hours after dropwise adding, cooling to room temperature, placing in a refrigerator at-10 ℃ for 8 hours, and filtering to obtain a light yellow filter cake; 150g of isopropanol and a filter cake are weighed and added into a 500mL single-neck flask, the mixture is stirred magnetically for 2 hours at 70 ℃ in a water bath under reflux, a yellow filter cake is obtained by suction filtration at 70 ℃, the filter cake is dried in vacuum for 24 hours at a low temperature, and 109.5g of purified oleamide propyl disulfobetaine is obtained, and the yield is 88.6%.
Example III
500G of erucamide propyl hydroxysulfobetaine and 0.5g of organic silicon defoamer are weighed, distilled for 1h under reduced pressure at 60 ℃, heated to 90 ℃ and distilled for 2h under reduced pressure, so as to obtain 165g of amber cream; 350g of isopropanol is added, the mixture is magnetically stirred for 2 hours at 70 ℃ in water bath under reflux, inorganic salts are removed by suction filtration at 70 ℃, and the filtrate is collected and placed in a refrigerator at minus 10 ℃ for overnight; the mixture is filtered under suction at low temperature to obtain a pale yellow filter cake, and the filter cake is dried under vacuum at low temperature for 12 hours to obtain 185g of purified fatty erucamide propyl hydroxysulfobetaine.
The etherification reaction is carried out by taking 45.58g of sodium bromoethyl sulfonate (216 mmol) and 50g of diethylene glycol dimethyl ether, stirring and dissolving uniformly to obtain 50% solution bromoethyl sodium sulfonate solution; weighing 101.2g (200 mmol) of purified stearic acid amide propyl hydroxysulfobetaine and 150g of diethylene glycol diethyl ether of diethylene glycol dimethyl ether 100g, uniformly mixing and stirring, then adding 12.1g (216 mmol) of potassium hydroxide, heating to 60-90 ℃ and alkalizing for 1h; dropwise adding a bromoethyl sodium sulfonate solution for 1.5h, continuously reacting for 3h after dropwise adding, cooling to room temperature, placing in a refrigerator at-10 ℃ for 8h, and performing suction filtration to obtain a light yellow filter cake; 200g of isopropanol and a filter cake are weighed and added into a 500mL single-neck flask, the mixture is stirred magnetically at 70 ℃ in a water bath under reflux for 2 hours, a yellow filter cake is obtained by suction filtration at 70 ℃, and the filter cake is dried in vacuum at a low temperature for 24 hours to obtain 120.7g of purified erucamide propyl disulfobetaine with the yield of 89.5%.
For the above example product validation, we formulated clean diverting acid using the fatty acid bis-sulfobetaine surfactant and purified fatty acid hydroxysulfobetaine prepared in examples 1-3, respectively, with a formulation of 2.4g surfactant +97.6g 20% hcl solution, as follows: 97.6g of 20% HCl solution and spindle magnet were added to a 250mL beaker2.4G of purified surfactant is added by starting magnetic low-speed stirring, the rotating speed is adjusted to 1000r/min, vortex closing time is recorded, then viscosity is tested every 5min until the viscosity is unchanged, and the viscosity in different disulfobetaine viscosity fresh acids in examples 1-3 are shown as follows:
TABLE 1 viscosity in different bis-sulfobetaine viscosity fresh acids
The diverting acids prepared in examples 1-3 were transferred to 2000mL beakers, respectively, and 4g, 8g, 12g, 20g, 24g, 30g of calcium carbonate powder were added in order, and the apparent viscosity was recorded
TABLE 2 viscosity after reaction of different disulfobetaine viscosities
Using the oleamide propyl disulfobetaine surfactant prepared in example 2, a clean diverting acid was formulated with a formulation of 2.4g of purified surfactant +94.6g of 20% HCl solution +3.0g of acidizing corrosion inhibitor BA1-11, 30g of calcium carbonate powder was added, and allowed to stand overnight for defoaming, and the rheological properties were tested and the rheological curves were as shown in FIG. 1.
The erucic acid amide propyl disulfobetaine surfactant and the erucic acid amide propyl hydroxysulfobetaine prepared in example 3 are used for preparing a cleaning diverting acid, the formula is 2.4g of a purifying surfactant, 94.6g of 20% HCl solution and 3.0g of an acidification corrosion inhibitor BA1-11, 30g of calcium carbonate powder is added, and the mixture is stood overnight for defoaming, so that the rheological property is tested, and the rheological curve is shown in fig. 2 and 3.
The invention aims at improving the dissolution performance, salt tolerance and temperature tolerance of a clean turning acid surfactant, combines the structure-activity relation of the structure and performance of the prior betaine surfactant, carries out chemical modification on the basis of the prior hydroxysulfobetaine, increases the steric hindrance of an inner salt six-membered ring, improves the solubility, and further increases the hydrophilicity and the salt tolerance of a double sulfo structure, thereby preparing the fatty acid amidopropyl double sulfo betaine for turning acidification.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. A method for synthesizing a clean turning acid betaine surfactant, which is characterized by comprising the following steps of: the structural formula of the betaine surfactant is as follows:
The synthesis steps are as follows, firstly, the fatty acid amidopropyl hydroxysulfobetaine is dehydrated, desalted and purified in sequence, then etherification reaction is carried out in a solvent, freeze suction filtration is carried out, and the fatty acid amidopropyl disulfobetaine is obtained after the desalting and purification.
2. A method of synthesizing a clean turning acid betaine surfactant according to claim 1, wherein: the fatty acid amidopropyl hydroxysulfobetaine is one of oleic acid amidopropyl hydroxysulfobetaine, stearic acid amidopropyl hydroxysulfobetaine and erucic acid amidopropyl hydroxysulfobetaine, the solid content is 40-50 wt%, and the isopropanol content is 20-30 wt%.
3. A method of synthesizing a clean turning acid betaine surfactant according to claim 1, wherein: the dehydration process comprises the steps of adding fatty acid amide propyl hydroxysulfobetaine and an organosilicon defoamer into a distillation flask, wherein the weight ratio of the fatty acid amide propyl hydroxysulfobetaine to the organosilicon defoamer is 900-1100:1, and carrying out rotary reduced pressure distillation for 1-5 h at 50-90 ℃ until no liquid is produced, thus obtaining yellow to succinic acid viscous paste.
4. A method of synthesizing a clean turning acid betaine surfactant according to claim 3, wherein: the desalting process comprises the steps of mixing dehydrated fatty acid amide propyl hydroxysulfobetaine with small molecular alcohol, heating to 40-80 ℃, stirring until the mixture is uniformly dispersed, filtering out inorganic salts while the mixture is hot, cooling to-10-0 ℃, filtering to obtain a pale yellow filter cake, and vacuum drying the filter cake at low temperature for 4-24 hours to obtain purified fatty acid amide propyl hydroxysulfobetaine.
5. A method of synthesizing a clean turning acid betaine surfactant according to claim 4, wherein: the etherification reaction comprises the steps of uniformly mixing and stirring purified fatty acid amide propyl hydroxysulfobetaine and a solvent, adding potassium hydroxide for alkalization for 1-4 h, heating to 60-90 ℃, dropwise adding an etherifying agent solution for 1-4 h, dropwise adding the etherifying agent solution, continuing to react for 1-4 h, cooling to-10-0 ℃, performing suction filtration to obtain a light yellow filter cake, desalting by using small molecular alcohol, performing suction filtration, and performing low-temperature vacuum drying for 4-24 h to obtain the purified fatty acid amide propyl disulfobetaine.
6. A method of synthesizing a clean turning acid betaine surfactant according to claim 4, wherein: the small molecular alcohol used in the desalting process step is one of methanol, ethanol and isopropanol, and the mass ratio of the small molecular alcohol to the fatty acid amide propyl hydroxysulfobetaine is 1-3:1.
7. A method of synthesizing a clean turning acid betaine surfactant according to claim 5, wherein: in the etherification reaction, the solvent is one of diethylene glycol dimethyl ether and diethylene glycol diethyl ether and a mixture thereof, and the mass ratio of the solvent to fatty acid amide propyl hydroxysulfobetaine is 1-3:1.
8. A method of synthesizing a clean turning acid betaine surfactant according to claim 5, wherein: in the etherification reaction, the mass ratio of the alkalizing reagent potassium hydroxide to the fatty acid amidopropyl hydroxysulfobetaine used in the alkalizing step is 1-1.1:1.
9. A method of synthesizing a clean turning acid betaine surfactant according to claim 5, wherein: in the etherification reaction, the etherifying agent is sodium bromoethyl sulfonate, and the mass ratio of the etherifying agent to the fatty acid amide propyl hydroxysulfobetaine is 1-1.1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410052683.9A CN117924124A (en) | 2024-01-15 | 2024-01-15 | Synthetic method of clean steering acid betaine surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410052683.9A CN117924124A (en) | 2024-01-15 | 2024-01-15 | Synthetic method of clean steering acid betaine surfactant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117924124A true CN117924124A (en) | 2024-04-26 |
Family
ID=90769532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410052683.9A Pending CN117924124A (en) | 2024-01-15 | 2024-01-15 | Synthetic method of clean steering acid betaine surfactant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117924124A (en) |
-
2024
- 2024-01-15 CN CN202410052683.9A patent/CN117924124A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109761823B (en) | Shale intercalation inhibitor prepared from low-molecular-weight branched quaternary ammonium salt | |
| CN107304161A (en) | A kind of laruyl alcohol alkyl ether and preparation method thereof and drilling fluid | |
| CN103145568A (en) | Cardanol cationoid quaternary ammonium salt and preparation method thereof | |
| CN102503863A (en) | Dialkyl ether disulfonate surfactant and preparation method thereof | |
| CN106111008A (en) | A kind of silicone betaines surfactant and preparation method thereof | |
| CN111333582A (en) | Imidazolyl organic molybdenum ionic liquid and preparation method thereof | |
| CN100415355C (en) | Polyoxyethylene chain three cation quaternary ammonium salt type surfactant and its sysnthesis method | |
| CN103880676B (en) | A kind of preparation method of dodecyl nipagin ester | |
| CN104437236A (en) | Preparation and purification methods of quaternary ammonium salt type dimeric surfactant | |
| CN102671700A (en) | Organic heteropoly acid hybrid catalyst for alcohol oxidation reaction and preparation method thereof | |
| CN104128120A (en) | Preparation method of cationic gemini surfactant with connection chain containing hydroxy group | |
| CN117924124A (en) | Synthetic method of clean steering acid betaine surfactant | |
| CN108586234B (en) | Preparation method of isooctanol polyoxypropylene ether fatty acid ester | |
| CN102698647A (en) | PH sensitive-type gemini surface active agents and synthesis method thereof | |
| CN109894050B (en) | Aryl ether sulfobetaine surfactant and preparation method thereof | |
| CN110368987B (en) | Preparation method and application of tree-like loofah sponge supported ionic liquid catalyst | |
| CN111073621A (en) | Double-long-chain anionic-non-composite surfactant for oil displacement and preparation method thereof | |
| CN103012176A (en) | Method for preparing long-chain alkyl 4-carboxyl anionic surfactant | |
| CN102389744A (en) | First class s-triazine amphoteric betaine surfactant and synthesizing method thereof | |
| US9957438B2 (en) | Compositions for, solutions for, and methods of use of siloxane based aromatic trisureas as viscosifiers | |
| CN103787847B (en) | A kind of take ionic liquid as the technique of solvent continuous production trimethyl orthoacetate | |
| US2991299A (en) | Titanium trialkanolamine derivatives | |
| CN112480036A (en) | Piperidine ionic liquid surfactant and preparation method thereof | |
| CN111454551A (en) | Application of imidazolyl molybdate ionic liquid in preparation of P LL A/I L s blend | |
| CN117511527B (en) | Descaling blocking remover and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |